Method of producing tarnish resistant copper and copper alloys and products thereof

Abstract

The instant invention comprises providing copper or a copper alloy which has on its surface a uniform glassy like and substantially pore free coating of copper phosphate, rinsing the coated material for at least two seconds in water at a pH of at least 8.0, at a temperature of 90°C to the boiling point and drying.

What is claimed is: 
     
       1. A method of producing a flexible laminate, comprising: A. providing a material selected from the group consisting of copper foil and copper sheet,   B. applying to a surface of said material a phosphoric acid solution of at least 8 percent concentration and containing from 3.5 grams per liter up to the solubility limit of a material selected from the group consisting of sodium dichromate and potassium dichromate and mixtures thereof, for at least 2 seconds, to form a uniform, glassy-like, substantially pore-free coating of copper phosphate from 20 to 1000 Angstroms thick, provided that when the concentration of phosphoric acid is increased, the minimum dichromate concentration is proportionately increased,   C. rinsing said material for at least 2 seconds in water at a pH of at least 8.0 and at a temperature from about 90°C up to the boiling point,   D. drying said material, and   E. adhesively laminating a plastic film to said surface.   
     
     
       2. A method according to claim 1 wherein said water is adjusted to said pH with a compound selected from the group consisting of the basic reaction salts of the alkali metals, the basic reaction salts of the alkaline earth metals, the hydroxides of the alkali metals, the hydroxides of the alkaline earth metals, ammonium salts with a basic reaction, ammonium hydroxide, and mixtures thereof. 
     
     
       3. A method according to claim 2 wherein said compound is calcium hydroxide and said pH is from 8.0 to 11.0. 
     
     
       4. A method according to claim 1 wherein following step B and prior to step C said material is rinsed in water with the pH unadjusted. 
     
     
       5. A method according to claim 1 wherein following step D and before step E said material is recrystallized annealed. 
     
     
       6. A method of producing a flexible laminate comprising: A. providing a material selected from the group consisting of copper foil and copper sheet,   B. oxidizing a surface of said material to form a surface oxide film from 150 to 1000 Angstrom units in thickness   C. applying a phosphoric acid solution of at least 8 percent concentration to said oxide film to form thereon a uniform, glassy-like, substantially porefree coating of copper phosphate,   D. rinsing said material for at least two seconds in water at a pH of at least 8.0, and at a temperature from 90°C up to the boiling point,   E. drying said material, and   F. adhesively laminating a plastic film to said surface.   
     
     
       7. A method according to claim 6 wherein said water is adjusted to said pH with a compound selected from the group consisting of the basic reaction salts of the alkali metals, the basic reaction salts of the alkaline earth metals, the hydroxides of the alkali metals, the hydroxides of the alkaline earth metals, ammonium salts with a basic reaction, ammonium hydroxide, and mixtures thereof. 
     
     
       8. A method according to claim 7 wherein said compound is calcium hydroxide and said pH is from 8.0 to 11.0. 
     
     
       9. A method according to claim 6 wherein following step C and prior to step D said material is rinsed in water with the pH unadjusted. 
     
     
       10. A method according to claim 6 wherein said plastic film is a polyester and said surface of said material is roughened to provide an average roughness peak of about one to 20 micro inches, RMS, prior to step B. 
     
     
       11. A method according to claim 6 wherein following step E and before step F said material is recrystallized annealed.